Burn protective materials

ABSTRACT

A method is described for reducing the afterflame of a flammable, meltable material. A textile composite is described comprising an outer textile comprising a flammable, meltable material, and a heat reactive material comprising a polymer resin-expandable graphite mixture.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of co-pending application U.S. Ser. No. 11/923,125, filed Oct. 24, 2007.

BACKGROUND OF THE INVENTION

In order to reduce fire related burn injuries, protective clothing is desired for professionals working in hazardous environments where short duration exposure to fire is possible, such as search and rescue, and police. Protective gear for workers exposed to these conditions should provide some enhanced protection to allow the wearer to get away from the hazard quickly and safely, rather than to combat the hazard.

Traditionally, flame resistant protective garments have been made with an outermost layer comprising non-combustible, non-melting fabric made of, for example, aramids, polybenzimidazole (PBI), poly p-phenylene-2,6-bezobisoxazole (PBO), modacrylic blends, polyamines, carbon, polyacrylonitrile (PAN), and blends and combinations thereof. These fibers may be inherently flame resistant but may have several limitations. Specifically, these fibers may be very expensive, difficult to dye and print, and may not have adequate abrasion resistance. Additionally, these fibers pick up more water and offer unsatisfactory tactile comfort as compared to nylon or polyester based fabrics.

For optimum user performance in environments with occasional flash fire exposure, a lightweight, breathable, waterproof, or water resistant garment with enhanced burn protection is desired. The cost of waterproof, flame resistant, protective clothing has been an important consideration for the large number of hazardous exposure applications outside fire protection, thereby precluding the use of typical, inherently flame resistant textiles such as those used in fire fighting community.

SUMMARY OF THE INVENTION

In one embodiment, a material is described that is suitable for use in garments for workers in hazardous environments, which is breathable, waterproof, and flame resistant, while being lightweight, comfortable to wear, flexible, and affordable. In one embodiment method is provided for reducing the afterflame of a flammable, meltable material to less than 20 seconds, comprising providing an outer textile comprising a flammable, meltable material, and comprising an inner side and an outer side; providing a heat reactive material comprising a polymer resin-expandable graphite mixture, wherein the expandable graphite has an expansion of at least 900 μm upon heating to 280° C.; applying the polymer-expandable graphite mixture to the inner surface of the outer textile material to form the heat reactive material, wherein the outer side of the outer textile is exposed to a flame.

DESCRIPTION OF THE DRAWINGS

The operation of the present invention should become apparent from the following description when considered in conjunction with the accompanying drawings, in which:

FIG. 1 is a schematic illustration of a cross-sectional view of one embodiment described herein.

FIG. 2 is a schematic illustration of cross-sectional view of another embodiment described herein.

FIG. 3 is a schematic illustrating one embodiment described herein.

FIG. 4 is a schematic illustration of another embodiment described herein.

FIG. 5 a is a schematic illustration of a polymer resin-expandable graphite applied as discrete dots.

FIG. 5 b is a schematic illustration of one embodiment of a pattern of applied in a grid.

FIG. 6 is a graphical representation of the expansion of expandable graphites.

FIG. 7 is a schematic representation of samples tested by the Horizontal Flame test described herein.

FIG. 8 is a schematic illustration of another embodiment described herein.

DETAILED DESCRIPTION OF THE INVENTION

In one embodiment, a method for reducing the afterflame of a flammable, meltable material is described herein. With reference to FIG. 1, a textile composite (2) comprising an outer textile (10) having a flammable, meltable material is provided with a heat reactive material (20) comprising a polymer resin-expandable graphite mixture. In one embodiment, the heat reactive material (20) is disposed on an inner side (11) of the outer textile (10). Upon exposure of the outer side (12) of the outer textile (10) to a flame, the outer textile provided with a layer of heat reactive material has an afterflame of less than 20 seconds, when tested according to the Horizontal Flame Test and Self-Extinguishing Test method provided herein. In a further embodiment of the present invention, optionally a thermally stable textile backer (14) is bonded, for example by the heat reactive material, to the textile composite (2) as illustrated in FIG. 1. Materials suitable for use as a thermally stable textile backer (14) include, for example, textiles which are not meltable according to the Melting and Thermal Stability Test as presented herein. Examples of suitable thermally stable textile backers include aramids, Flame Resistant (FR) cottons, PBI, PBO, FR rayon, modacrylic blends, polyamines, carbon, fiberglass, PAN, polytetrafluoroethylene (PTFE), and blends and combinations thereof. Textiles which are meltable according to the Melting and Thermal Stability Test are suitable as an outer textile including but not limited to nylon 6, nylon 6,6, polyester, polypropylene.

In another embodiment, a method is provided for reducing the break-open time of a textile composite. With reference to one embodiment illustrated in FIG. 2, a textile composite (2) is provided comprising an outer textile (10) having a meltable material which may be either flammable or inflammable. A thermally stable convective barrier (30) is further provided next to an inner side (11) of the outer textile (10), and a heat reactive material (20) provided therebetween. In one method, a textile composite (2) is formed having a break-open time that is increased by at least 20 seconds over a textile composite constructed of substantially the same materials in which no heat reactive material is incorporated, when tested according to the method for Horizontal Flame Test described herein. Embodiments comprising textile composites may be made according to the methods herein and having an outer textile (10) comprising a meltable material and a heat reactive material (20) wherein the textile composite has an increased break-open time that is greater than about 30 seconds when tested according to the Horizontal Flame test method described herein.

In one embodiment, a method for making a textile composite is provided in which a textile composite having an outer textile (10) which comprises a material that is both meltable and flammable, and which further comprises a thermally stable convective barrier (30) and a heat reactive material (20) between the outer textile and the thermally stable convective barrier, has an increase in break-open time and a decrease in afterflame, when compared to substantially the same textile composites formed without a heat reactive material. The break-open and afterflame times are tested according to the test methods for Horizontal Flame Test and Self-Extinguishing Test, respectively, provided herein. In one such embodiment, a textile composite has a break-open time that is greater than 20 seconds and an afterflame of less than 20 seconds.

In a further embodiment, as exemplified in FIG. 3, the textile composite (2) may comprise a multilayer thermally stable convective barrier (30). The thermally stable convective barrier (30) may comprise two or more layers of a thermally stable film (34 and 34′) and, for example a polymer layer (35) therebetween. The polymer layer (35) may be waterproof or air impermeable or both.

In another embodiment, such as the one illustrated in FIG. 4, the textile composite (2) may further comprise a textile backer (50) positioned on a side of the thermally stable convective barrier (30) that is opposite the heat reactive material (20). The textile backer (50) may be attached to the textile composite with an adhesive (40). Preferably, the backer textile (50) is a thermally stable textile backer, such as a material which passes melting and thermal stability test described herein.

A method is also provided for reducing the predicted percent body burn after exposure to flame when tested according to the ASTM F1930 Garment Flammability Test (Pyroman) described herein. The method comprises providing a textile composite comprising an outer textile comprising a meltable material and a thermally stable convective barrier, having a heat reactive material between the outer textile and the thermally stable convective barrier. The method further comprises constructing a garment from the textile composite wherein the outer textile is oriented to face away from the body of the mannequin and toward the source of the flame. After a 4 second exposure during the Garment Flammability Test, a reduction in body burn, afterflame and melt dripping is achieved compared to a garment constructed similarly and with substantially the same materials but without a heat reactive material between the outer textile and the thermally stable convective barrier. In certain embodiments, melt dripping is not observed, afterflame is reduced by about 20 seconds and/or a garment having the heat reactive material has a predicted percent body burn that is about 5 percentage points lower than a garment constructed without the heat reactive material.

FIG. 6 is a graphic representation of the TMA expansion rates of several expandable graphites (A=Nyagraph 351 available from Nyacol Nano technologies, Inc; B=3626 available from Asbury Graphite Mills Inc., C=3494 Asbury Graphite Mills Inc, D=Nyagraph 35 available from Nyacol Nano technologies, Inc.; E=3538 available from Asbury Graphite Mills Inc.). An expandable graphite most suitable for use in methods disclosed herein has average expansion rate of at least 9 μm/° C. between about 180° C. and 280° C. Depending on the desired properties of the textile composite, it may be desirable to use an expandable graphite having an expansion rate greater than 9 μm/° C. between about 180° C., or on expansion rate greater than 12 μm/° C. between about 180° C. and 280° C., or an expansion rate greater than 15 μm/° C. between about 180° C. and 280° C. One expandable graphite suitable for use in certain embodiments expands by at least 900 microns in TMA expansion test described herein when heated to about 280° C. Another expandable graphite suitable for use in certain embodiments expands by at least 400 microns in TMA expansion test described herein when heated to about 240° C. Expandable graphite particle size suitable for present invention should be chosen so that the polymer resin-expandable graphite mixture may be applied with the selected application method. For example, where the polymer resin-expandable graphite mixture is applied by a gravure printing techniques, the expandable graphite particle size should be small enough to fit in the gravure cells.

Polymer resins having a melt or softening temperature of less than 280° C. are suitable for use in disclosed embodiments. In one embodiment polymer resins used in methods described herein are sufficiently flowable or deformable to allow the expandable graphite to expand substantially upon heat exposure at or below 300 C, preferably at or below 280° C. It may be desirable that the extensional viscosity of a polymer resin is low enough to allow for the expansion of expandable graphite and high enough to maintain the structural integrity of the heat reactive material after expansion of the mixture of polymer resin and expandable graphite. In another embodiment a polymer resin is used which has a storage modulus between 10³ and 10⁸ dyne/cm² and Tan delta between about 0.1 and about 10 at 200° C. In another embodiment a polymer resin is used that has a storage modulus between 10³ and 10⁶ dyne/cm². In another embodiment a polymer resin is used that has a storage modulus between 10³ and 10⁴ dyne/cm². Polymer resins suitable for use in some embodiments have a modulus and elongation at around 300 C or less, suitable to allow the graphite to expand. Polymer resins suitable for use in some embodiments are elastomeric. Other polymer resins suitable for use in some embodiments are cross-linkable, such as crosslinkable polyurethane such as Mor-melt R7001E (from Rohm & Haas). In other embodiments, suitable polymer resins are thermoplastic having a melt temperature between 50° C. and 250° C., such as Desmomelt VP KA 8702 (from Bayer Material Science LLC). Polymer resins suitable for use in embodiments described herein comprise polymers which include but are not limited to polyesters, thermoplastic polyurethanes and crosslinkable polyurethanes, and combinations thereof. Other polymer resins may comprises one or more polymers selected from polyester, polyamide, acrylic, vinyl polymer, polyolefin. Other polymer resins may comprise silicone or epoxy. Flame retardant materials optionally may be incorporated in the polymer resin.

In some embodiments of the polymer resin-expandable graphite mixture, the mixture, upon expansion, forms a plurality of tendrils comprising expanded graphite. The total surface area of the polymer resin-expandable graphite mixture increases significantly when compared to the same mixture prior to expansion. In one embodiment, the surface area of the mixture is increased at least five times after expansion. In another embodiment, the surface area of the mixture is increases at least ten times after expansion. In addition, tendrils will often extend outward from the expanded mixture. Where the polymer resin-expandable graphite mixture is situated on a substrate in a discontinuous form, the tendrils will extend to at least partially fill the open areas between the discontinuous domains. In a further embodiment, the tendrils will be elongated, having a length to width aspect ratio of at least 5 to 1.

The polymer resin-expandable graphite mixture may be produced by a method that provides an intimate blend of polymer resin and expandable graphite, without causing substantial expansion of the expandable graphite. Suitable mixing methods include but not limited to paddle mixer, blending and other low shear mixing techniques. In one method, the intimate blend of polymer resin and expandable graphite particles is achieved by mixing the expandable graphite with a monomer or prepolymer prior to polymerization of the polymer resin. In another method, the expandable graphite may be blended with a dissolved polymer, wherein the solvent in removed after mixing. In another method, expandable graphite is blended with a hot melt polymer at a temperature below the expansion temperature of the graphite and above the melting temperature of the polymer. In methods which provide an intimate blend of polymer resin and expandable graphite particles or agglomerates of expandable graphite, the expandable graphite is coated or encapsulated by the polymer resin prior to expansion of the graphite. In other embodiments, the intimate blend is achieved prior applying the polymer resin-expandable graphite mixture to a substrate.

The polymer resin-expandable graphite mixture comprises less than or equal to about 50 wt %, or less than or equal to about 40 wt %, or less than or equal to about 30 wt % expandable graphite based on the total weight of the polymer resin-expandable graphite mixture, and the balance substantially comprising the polymer resin. In other embodiments, the expandable graphite comprises less than or equal to about 20 wt %, or less than or equal to about 10 wt %, or less than or equal to about 5 wt % of the mixture, and the balance substantially comprising the polymer resin. Generally, from about 5 wt % to 50 wt % of expandable graphite based on the total weight of the polymer resin-expandable graphite mixture, is desired. In some embodiments, desirable flame resistance performance may be achieved with even lower amounts of expandable graphite. Loadings as low as 1% may be useful. Depending on the properties desired and the construction of the resulting textile composites, other levels of expandable graphite may also be suitable for other embodiments. Other additives such as pigments, fillers, antimicrobials, processing aids and stabilizers may also be added to the mixture.

The polymer resin-expandable graphite mixture may be applied to the outer textile (10) of the textile composite to form the heat reactive material (20) such as exemplified in FIG. 1. The heat reactive material may be applied as a continuous layer. However, where enhanced breathability and/or hand is desired, the polymer resin-expandable graphite mixture may be applied discontinuously to form a layer of heat reactive material having less than 100% surface coverage. A discontinuous application may provide less than 100% surface coverage by forms including but not limited to dots, grids, lines, and combinations thereof. In some embodiments with discontinuous coverage, the average distance between adjacent areas of the discontinuous pattern is less than 5 mm, and preferably less than 3.5 mm, 2.5 mm, 1.5 mm, and 0.5 mm. For example, in a dot pattern printed onto a substrate, the spacing between the dots would be measured. In embodiments where properties such as hand, breathability, and/or textile weight are important, a surface coverage of less than about 90%, or less than about 80%, or less than about 70%, or less than about 60%, or less than about 50%, or less than about 40%, or less than about 30% may be used. One method for achieving a coverage of less than 100% comprises applying the polymer resin-expandable graphite mixture by printing the mixture onto a surface of the construct by, for example gravure printing. FIGS. 5 a and 5 b illustrate examples in which the layer of heat reactive material (20) is provided in patterns of dots (5A) and grids (5B) as the polymer resin-expandable graphite mixture (20) is applied discontinuously to form a heat reactive material, for example to a substrate (10) such as a thermally stable convective barrier or to the inner side of an outer textile. The polymer resin-expandable graphite mixture may be applied to achieve an add-on weight of between about 10 gsm to about 100 gsm of the mixture. In some embodiments, the mixture is applied to the substrate to achieve an add-on weight of less than 100 gsm, or less than 75 gsm, or less than 50 gsm, or less than 25 gsm.

In one discontinuous application, such as in the application of discrete dots (20) in FIG. 5A, the polymer resin-expandable graphite mixture is applied to a substrate forming a layer of heat reactive material (20) in the form of a multiplicity of discrete pre-expansion structures comprising the polymer resin-expandable graphite mixture. Upon expansion, the discrete dots form a multiplicity of discrete expanded structures having structural integrity thereby providing sufficient protection to a textile composite to achieve the enhanced properties described herein. By structural integrity it is meant that the heat reactive material after expansion withstands flexing or bending without substantially disintegrating or flaking off the substrate, and withstands compression upon thickness measurement when measured according to the Thickness Change Test described herein.

The polymer resin-expandable graphite mixture may be applied in other forms in addition to dots, lines, or grids. Other methods for applying the polymer resin-expandable graphite mixture may include screen printing, or spray or scatter coating or knife coating, provided the polymer resin-expandable graphite mixture may be applied in a manner in which the desired properties upon exposure to heat or flame are achieved.

In one embodiment comprising a thermally stable convective barrier, as exemplified in FIG. 2, the layer of heat reactive material (20) may be disposed on the outer textile (10) or on the thermally stable convective barrier (30). In one preferred method, the polymer resin-expandable graphite mixture is applied in a manner in which the mixture provides a good bond between the thermally stable convective barrier and the outer textile. In embodiments where the textile composite comprises a laminate construction, the polymer resin-expandable graphite mixture is applied as an adhesive, for example, to bond the inner side of outer textile layer (10) and the thermally stable convective barrier (30) forming a layer of heat reactive material between the outer textile layer (10) and the thermally stable convective barrier (30). In another method, the polymer resin-expandable graphite mixture is applied to the composite forming a layer of heat reactive material which may optionally be disposed at least partially within surface pores or surface voids of one or both of the layers (10 and 30).

The methods described provide enhanced properties which are particularly beneficial to textile composites comprising an outer textile (10) which comprises materials comprising non-flammable meltable materials or flammable meltable materials. Meltable materials are materials that are meltable when tested according to the Melting and Thermal Stability test. Materials are tested with the Vertical Flame test to determine whether they are flammable or nonflammable. In certain embodiments, the outer textile comprises a polyamide such as nylon 6 or nylon 6,6, and polyester, polyethylene, and combinations thereof. Preferred textile composites are comprised of outer textiles which are knit or woven, and the outer textile has a weight of less than 10.0 oz/yd2, preferably between 1 oz/yd2 and 10 oz/yd2. Alternately, the outer textile weight is between 1 oz/yd2 and 5.0 oz/yd2.

Thermally stable convective barrier materials may be provided to the textile composite to further enhance the performance of the textile composite upon exposure to flame or heat. Thermally stable convective barrier materials comprise materials such as a heat stable film, and include materials such as polyimide, silicone, PTFE, such as dense PTFE or expanded PTFE. The thermally stable convective barrier prevents the convective heat transfer to the layers behind it when exposed to a convective heat source. Convective barriers for use in embodiments described herein have a maximum air permeability of less than about 10 Frazier after thermal exposure when tested as per the method described herein. Preferably, a convective barrier has an air permeability after thermal exposure of less than 5 Frazier. More preferably, a convective barrier has an air permeability after thermal exposure of less than 3 Frazier.

Textile composites made according to the methods described herein preferably have an MVTR greater than about 1000, or greater than about 3000, or greater than about 5000, or greater than about 7000, or greater than about 9000, or greater than about 10000, or higher. Preferred textile composites have a break open time greater than about 50 seconds, greater than about 60 seconds, or even greater than 120 seconds when tested according to the methods for Horizontal Flame Test described herein. Preferable textile composites also have an after flame less than 20 seconds when tested according to the Horizontal Flame Test and Self-Extingishing Test methods described herein. Further preferred textile composites have an afterflame less than 15 seconds, or less than 10 seconds, or less than 5 seconds. Preferred textile composites exhibit substantially no melt dripping behavior when tested in the Horizontal Flame test. In another embodiment, a textile composite is formed according to the methods described herein, having a hand less than about 300, or less than about 250, or less than about 200, and having an after-flame of less than about 20 seconds, or less than about 15 seconds or less than about 10 seconds, or an after-flame of about zero, when measured according to the tests described herein for Flexibility and Hand, and Horizontal Flame Test and Self-Extinguishing Test.

In an embodiment of the current invention, the meltable materials, for example an outer textile (10), described may combine with the expanding heat reactive material (20) during exposure to heat and/or flame that is sufficient to melt the meltable materials to form an expanded composite. In some embodiments, the meltable material may be sufficiently drawn in to or adsorbed on at least a portion of the expanding heat reactive material. The resulting expanded composite may comprise the elongated tendrils of the heat reactive material and the meltable material. In some embodiments, the expanded composite has structural stability when tested in accordance to the Thickness Change Test. In one embodiment, the textile composite of the present invention changes thickness upon heat exposure. The thickness of the textile composite after expansion is at least 1 mm greater than the thickness of the textile composite prior to expansion.

In one embodiment, a material is described that is suitable for use in garments for workers in hazardous environments, which is breathable, waterproof, and flame resistant, while being lightweight, flexible, and comfortable to wear.

Without intending to limit the scope of the present invention, the following examples illustrate how the present invention may be made and used:

TEST METHODS

Horizontal Flame Test

This test is modeled generally after MIL-C 834298. A 75 mm by 250 mm textile composite sample (3 inch by 10 inch) was clamped in a steel fixture (400 mm long by 75 mm wide with a center window of about 350 mm long and 50 mm wide) using binder clips. The sample was clamped in a manner that secured the edges of the textile composite without obstructing the area of textile composite present in the window of the steel clamping fixture. The sample in fixture was placed horizontally at a height of about 40 mm in a 90 mm flame (based on butane at 2 psi using a Meeke burner). FIG. 7 depicts the orientation of the textile composite construction 2, wherein the meltable outer textile 10 is oriented adjacent to the flame 70 during testing. The sample is exposed to the flame and the time is recorded until the convective barrier breaks open (or a hole forms in the face textile in case where convective barrier is not used), either by cracking or the formation of a hole, and light from the flame is evident when viewing through the crack or opening in the material. The sample is subsequently removed from the flame. The time recorded is referred to as the horizontal flame break open time. The sample is observed for melt dripping or falling droplets.

Self-Extinguishing Test

After the material sample is removed from the flame in the Horizontal Flame Test, above, the material is observed for any after flame and afterflame time is recorded. If the sample exhibits any melt dripping or falling droplets, it is also recorded. If no after flame is observed, or if an after flame is observed upon removal but extinguishes within five (5) seconds after removal from the flame, the material is said to be self-extinguishing.

Vertical Flame Test

Outer textile material samples were tested in accordance with ASTM D6413 test standard. Samples were exposed to flame for 12 seconds. After-flame time was averaged for 3 samples. Textiles with after-flame of greater than 2 seconds were considered as flammable.

Garment Flammability Test Method

Test garments were evaluated for resistance to a simulated flash fire exposure employing procedures similar to ASTM F 1930-00 Standard Test Method for Evaluation of Flame Resistant Clothing for Protection Against Flash Fire Simulations Using an Instrumented Manikin. Prior to testing, a nude manikin calibration was done with a four seconds exposure. After calibration, a cotton t-shirt (size 42 regular, weighing less than 7 oz/yd2) and a cotton short (size M) were put on followed by the jacket made of laminates described below (size 42 regular). After dressing the manikin, a sophisticated computer system was used to control the test procedure, to include the lighting of pilot flames, exposing the test garment to the flash fire, acquisition of data for 120-seconds, followed by running the exhaust fans to vent the chamber. Data acquired by the system was used to calculate the incident heat flux, predicted burn injury for each sensor during and after the exposure, and produce a report and graphics for each test. Any continued flaming after exposure was noted as afterflame and melt dripping or falling of droplets was also noted. The predicted burn injury data along with afterflame and melt dripping observations is reported in Table 3. The predicted burn injury is calculated by dividing the total number of sensors that reach 2^(nd) and 3^(rd) degree burn by the number of sensors in the area covered by the test garment. The total percent body burn reported is the sum of the 2^(nd) and 3^(rd) degree burn percentages.

Melting and Thermal Stability Test

The test was used to determine the thermal stability of textile materials. This test is based on thermal stability test as described in section 8.3 of NFPA 1975, 2004 Edition. The test oven was a hot air circulating oven as specified in ISO 17493. The test was conducted according to ASTM D 751, Standard Test Methods for Coated Fabrics, using the Procedures for Blocking Resistance at Elevated Temperatures (Sections 89 to 93), with the following modifications:

-   -   Borosilicate glass plates measuring 100 mm×100 mm×3 mm (4 in.×4         in.×⅛ in.) were used.     -   A test temperature of 265° C., +3/−0° C. (510° F., +5/−0° F.)         was used.

The specimens were allowed to cool a minimum of 1 hour after removal of the glass plates from the oven.

Any sample side sticking to glass plate, sticking to itself when unfolded, or showing evidence of melting or dripping was considered as meltable. Any sample side lacking evidence of meltable side was considered as thermally stable.

Moisture Vapor Transmission Rate (MVTR)

A description of the test employed to measure moisture vapor transmission rate (MVTR) is given below. The procedure has been found to be suitable for testing films, coatings, and coated products.

In the procedure, approximately 70 ml of a solution consisting of 35 parts by weight of potassium acetate and 15 parts by weight of distilled water was placed into a 133 ml polypropylene cup, having an inside diameter of 6.5 cm at its mouth. An expanded polytetrafluoroethylene (PTFE) membrane having a minimum MVTR of approximately 85,000 g/m²/24 hrs. as tested by the method described in U.S. Pat. No. 4,862,730 (to Crosby), was heat sealed to the lip of the cup to create a taut, leakproof, microporous barrier containing the solution.

A similar expanded PTFE membrane was mounted to the surface of a water bath. The water bath assembly was controlled at 23° C. plus 0.2° C., utilizing a temperature controlled room and a water circulating bath.

The sample to be tested was allowed to condition at a temperature of 23° C. and a relative humidity of 50% prior to performing the test procedure. Samples were placed so the microporous polymeric membrane was in contact with the expanded polytetrafluoroethylene membrane mounted to the surface of the water bath and allowed to equilibrate for at least 15 minutes prior to the introduction of the cup assembly.

The cup assembly was weighed to the nearest 1/1000 g and was placed in an inverted manner onto the center of the test sample.

Water transport was provided by the driving force between the water in the water bath and the saturated salt solution providing water flux by diffusion in that direction. The sample was tested for 15 minutes and the cup assembly was then removed, weighed again within 1/1000 g.

The MVTR of the sample was calculated from the weight gain of the cup assembly and was expressed in grams of water per square meter of sample surface area per 24 hours.

Weight

Weight measurements on materials were conducted as specified in ASTM D751, section 10.

Thickness Change Test

Samples were tested for initial thickness as per ASTM D751, section 9 with the exception that the pressure foot diameter was 1″. The instrument was adjusted to apply a pressure force of approximately 3.4 psi to the specimen. After exposure to Horizontal Flame Test for 60 seconds (or after break-open if break-open occurred prior to 60 seconds), the sample was remeasured for thickness change. Thickness and integrity of the expanded structure were observed after testing.

Air Permeability Test of Thermally Stable Convective Barrier

Preferably, a convective barrier has an air permeability after thermal exposure of less than 5 Frazier. To determine the thermal stability of a convective barrier, a 381 mm (15 in.) square fabric specimen was clamped in a metal frame and then suspended in a forced air-circulating oven at 260° C. (500° F.). Following a 5-minute exposure, the specimen was removed from the oven. After allowing the specimen to cool down, the air permeability of the specimen was tested according to test methods entitled ASTM D 737-75. “Standard Test Method for AIR PERMEABILITY OF TEXTILE FABRICS.” Specimens with less than 5 Frazier were considered as a thermally stable convective barrier.

Thickness of Convective Barrier

Convective barrier thickness was measured by placing the membrane between the two plates of a Kafer FZ1000/30 thickness snap gauge (Käfer Messuhrenfabrik GmbH, Villingen-Schwenningen, Germany). The average of three measurements was used.

Density of Convective Barrier

Samples die cut to form rectangular sections 2.54 cm by 15.24 cm were measured to determine their mass (using a Mettler-Toledo analytical balance Model AG204) and their thickness (using a Kafer FZ1000/30 snap gauge). Using these data, density was calculated with the following formula:

$\rho = \frac{m}{w*l*t}$ in which: ρ=density (g/cc); m=mass (g); w=width (cm); l=length (cm); and t=thickness (cm). The average of the three measurements was used. Expansion Test

TMA (Thermo-mechanical analysis) was used to measure the expansion of expandable graphite particles. Expansion was tested with TA Instruments TMA 2940 instrument. A ceramic (alumina) TGA pan, measuring roughly 8 mm in diameter and 12 mm in height was used for holding the sample. Using the macroexpansion probe, with a diameter of roughly 6 mm, the bottom of the pan was set the zero. Then flakes of expandable graphite about 0.1-0.3 mm deep, as measured by the TMA probe, were put in the pan. The furnace was closed and initial sample height was measured. The furnace was heated from about 25° C. to 600° C. at a ramp rate of 10° C./min. The TMA probe displacement was plotted against temperature; the displacement was used as a measure of expansion.

Flexibility or Hand Measurement

Hand measurements of textile composite samples were obtained using a Thwing-Albert Handle-o-meter, (model # 211-5 from Thwing Albert Instrument Company, Philadelphia, Pa.) Lower values indicate lower load required to bend the samples and indicates more flexible sample.

EXAMPLES

Thermally Stable Convective Barrier 1

Thermally Stable Convective Barrier 1 was constructed by treating ePTFE membrane (0.3 micron average pore size and 0.3 g/cc density) with a coating comprised of a fluoroacrylate polymer and carbon black as taught in U.S. Patent Application Publication No/2007/0009679.

Thermally Stable Convective Barrier 2

A thermally stable convective barrier 2 was constructed by treating ePTFE film having 0.3 micron pore size and 0.45 g/cc density with a continuous, partially penetrated layer of 15 gsm of a breathable, moisture cured polyurethane in accordance with the teachings of U.S. Pat. No. 4,194,041. A second ePTFE membrane identical to the first was brought in contact with the polyurethane coated side of the aforementioned coated ePTFE and combined in a nip to form a tri-component ePTFE film. The film was partially cured in oven and then allowed to fully cure on a cardboard core at about >50% RH for 7 days

Polymer Resin (PR) 1

A flame retardant polyurethane resin was prepared by first forming a resin in accordance with the examples of commonly owned U.S. Pat. No. 4,532,316, and adding in the reactor a phosphorus-based additive (Antiblaze PR82) in an amount of about 20% by weight.

Polymer Resin—Expandable Graphite Mixture 1

A mixture of a polymer resin and expandable graphite was prepared by mixing about 20 gm of an expandable graphite (Grade 3626 from Asbury Graphite Mills, Inc having an expansion of greater than 900 μm upon heating to 280° C.) to about 80 gm of Polymer Resin (PR) 1. Mixing of expandable graphite flakes into the polymer resin was carried out at about 100° C. using a low shear hand mixer for at least 1 minute to ensure uniform dispersion.

Polymer Resin—Expandable Graphite Mixture 2

A mixture of polymer resin and expandable graphite was prepared by mixing about 5 gm of an expandable graphite (Grade 3626 from Asbury Graphite Mills, Inc) to about 95 gm of PR 1. Mixing was carried out as described above.

Polymer Resin—Expandable Graphite Mixture 3

A polymer resin prepared in accordance with U.S. Pat. No. 4,532,316. About 20 gm of an expandable graphite (Grade 3626 from Asbury Graphite Mills, Inc) was added to about 80 gm of polymer resin to get polymer resin-expandable graphite mixture 3. Mixing was carried out as described above.

Polymer Resin—Expandable Graphite Mixture 4

A polymer resin prepared in accordance with U.S. Pat. No. 4,532,316. About 20 gm of an expandable graphite (Grade Nyagraph 351 having an expansion of greater than 900 μm upon heating to 280° C. available from Nyacol Nano technologies, Inc Ashland, Mass.) was added to about 80 gm of polymer resin to get polymer resin-expandable graphite mixture 4. Mixing was carried out as described above.

Polymer Resin-Ammonium Polyphosphate Mixture

A mixture was prepared by adding about 20 gm of ammonium polyphosphate (FR CROS C30 available from Flame Chk, Inc.) to about 80 gm of PR1. Mixing was carried out as described above.

Polymer Resin—Three Component Intumescent

A mixture was prepared by adding about 20 gm of commercially available three component chemical intumescent (Budit 3076 available from FlameChk, Inc.) to about 80 gm of PR1. Mixing was carried out as described above.

Polymer Resin—Expandable Graphite Mixture 5

A mixture was prepared by adding about 20 gm of expandable graphite (grade 3538 from Asbury Graphite Mills, Inc., having an expansion of less than 900 μm at 280° C.) to about 80 gm of PR1. Mixing was carried out as described above.

Waterproof Film 1

A commercially available waterproof breathable monolithic thermoplastic polyurethane film sold by Omniflex (Greenfield, Mass.) under part number 1540 was used.

Fabric Example 1

A textile comprising heat reactive material was prepared as follows. A 130 gsm nylon 6,6 knit outer textile (10) from Milliken Corporation, Spartanburg, S.C. (STYLE 755133) was coated with discrete dots of the polymer resin-expandable graphite mixture 1 by a gravure roller (at about 100° C. with a pressure of about 40 psi) in such a manner as to provide coverage of approximately 32 percent on the surface of the fabric, with a laydown of about 35 grams per square meter (gsm). The gravure roll had a round dot pattern with a cell depth about 1200 um, cell opening of about 2500 um, and a spacing of about 2500 um.

The coated fabric was allowed to cure at 50% RH and 23° C. for 48 hours.

Samples of the textile coated with the polymer resin-graphite mixture 1 were tested as per self extinguishing test described herein recorded an afterflame of less than 5 seconds.

Laminate Example 1

A laminate was made using a 95 gsm nylon 6,6 plain weave outer textile from Milliken (part number 131967) and thermally stable convective barrier 1, substantially as depicted in FIG. 2. The laminate was constructed by printing discrete dots of the Polymer Resin—Expandable Graphite Mixture 1 onto thermally stable convective barrier 1 and then adhering the 95 gsm nylon woven outer textile to the thermally stable convective barrier using a nip pressure of about 30 psi. The discrete dots of heat reactive material (20) were printed by a gravure roller as described above.

The resultant laminate was a two layer laminate of a thermally stable convective barrier and a nylon woven meltable outer textile layer bonded by dots of polymer resin-expandable graphite mixture 1. The laminate was taken up onto a steel drum under tension and allowed to cure for about 48 hours at greater than about 50% relative humidity.

Samples were tested according to MVTR, Horizontal Flame Test and Self-Extinguishing Test methods, described herein and reported in Table 1.

Laminate Example 2

A two layer laminate was made substantially according to Example 1, except that thermally stable convective barrier 2, described above, was used in place of thermally stable convective barrier 1

Samples were tested according to the Horizontal Flame Test and Self-Extinguishing Test methods, described herein and reported in Table 1.

Laminate Example 3

A laminate was prepared substantially as depicted in FIG. 4, and was made using a 130 gsm nylon 6,6 circular knit outer textile (10) from Milliken Corporation, Spartanburg, S.C. (STYLE 755133), and thermally stable convective barrier 1 (30). The laminate was constructed by printing discrete dots of polymer resin-expandable graphite mixture 1 onto the thermally stable convective barrier 1 (30) then adhering 130 gsm nylon 6,6 circular knit outer textile (10) to the thermally stable convective barrier 1 (30) using a nip. The gravure lamination process was carried out as described in laminate example 1. The resultant laminate was a two layer laminate of a thermally stable convective barrier and a nylon knit meltable face textile layer bonded by dots of polymer resin-expandable graphite mixture. The laminate was taken up onto a steel drum under tension and allowed to cure for about 48 hours at greater than about 50% relative humidity

Samples were tested according to the Horizontal Flame Test and Self-Extinguishing Test methods, described herein and reported in Table 1.

Laminate Example 4

A laminate made substantially according to Example 3 was provided and PR1 was applied in a discrete dot pattern (about 15 gsm) to the exposed side of the thermally stable convective barrier (the side opposite the nylon woven textile), as depicted in FIG. 4. A 60 gsm aramid knit backer textile (50) (Part No. KRDZ602 from SSM Industries) was then adhered to the two layer laminate by feeding the two layer laminate with the PR1 dots and the aramid backer through an additional nip to form a three layer laminate. The three layer laminate was then taken up onto a steel drum under tension and allowed to cure for about 48 hours at greater than about 50% relative humidity.

Samples were tested according to the Horizontal Flame Test and Self-Extinguishing Test methods, described herein and reported in Table 1. Samples were also tested for flexibility as per hand test and showed good flexibility with hand result of 192.

Laminate Example 5

A three layer laminate was prepared substantially in accordance with Example 4, except that a 109 gsm Modacrylic/Cotton knit fabric (Part No. 05289 from United Knitting) was used as backer textile instead of the aramid knit backer textile.

Samples were tested according to the Horizontal Flame Test and Self-Extinguishing Test methods, described herein and reported in Table 1.

Laminate Example 6

A three layer laminate was made substantially in accordance with Example 4, except that a 80 gsm Polyester woven (Part No. US101 from Milliken Corporation) was used as the outer textile instead of a 130 gsm nylon 6,6 knit outer textile.

Laminate Example 7

A two layer laminate was prepared substantially in accordance with Example 2, except that Polymer resin-Expandable Graphite Mixture 2 was used instead of Polymer resin-Expandable Graphite Mixture 1.

Laminate Example 8

A two layer laminate was prepared substantially in accordance with Example 3, except that gravure roll print covered approximately 89% of thermally stable convective barrier 1 and Polymer resin-Expandable Graphite Mixture 4 was used.

Laminate Example 9

A three layer laminate was prepared substantially in accordance with Example 4, except that Polymer resin-Expandable Graphite 3 was used.

As shown in Table 1, the test results on Laminate Examples 1 through 9 show the present invention may achieve improved break-open time, substantially no after-flame, no melt dripping while providing good moisture vapor transmission rates. Additional examples described below were created to further explore the effect of laminate constructions and materials.

Example 10

A laminate was made using a 95 gsm nylon 6,6 plain weave outer textile from Milliken (part number 131967), and thermally stable convective barrier 1. The laminate was constructed by printing discrete dots of PR1 onto the thermally stable convective barrier 2 then adhering the 95 gsm nylon outer textile to the thermally stable convective barrier using a nip. The resultant laminate created was a two layer laminate of the thermally stable convective barrier (30) and the nylon woven meltable outer textile (10) bonded by PR1 (40). The laminate was taken up onto a steel drum under tension and allowed to cure for about 48 hours at greater than about 50% relative humidity.

Samples were tested according to the Horizontal Flame Test and Self-Extinguishing Test methods, described herein and reported in Table 1.

Example 11

A laminate was constructed in same manner as the laminate of Example 4, except that Polymer Resin-Ammonium Polyphosphate Mixture was used in place of active insulative material 1 when forming the two layer laminate portion of the three layer laminate.

Samples were tested according to the Horizontal Flame Test and Self-Extinguishing Test methods, described herein and reported in Table 1.

Example 12

A laminate was constructed in same manner as the laminate of Example 4, except that Polymer Resin-Three Component Intumescent Mixture was used instead of Polymer resin-Expandable Graphite Mixture 1 when forming the two layer laminate.

Samples were tested according to the Horizontal Flame Test and Self-Extinguishing Test methods, described herein and reported in Table 1. Samples were also tested for flexibility and hand value obtained was 198.

Example 13

A laminate was constructed in same manner as the laminate of Example 4, except that Polymer resin-Expandable Graphite Mixture 5 was used instead of Polymer resin-Expandable graphite Mixture 1 for making the two layer laminate portion of the three layer laminate.

Samples were tested according to the Horizontal Flame Test and Self-Extinguishing Test methods, described herein and reported in Table 1. Samples were also tested for flexibility and hand value obtained was 171.

Example 14

A laminate was constructed in same manner as Example 3, except that a waterproof breathable polyurethane film was used in place of thermally stable convective barrier 1. A commercially available breathable monolithic thermoplastic polyurethane film sold by Omniflex (Greenfield, Mass.) under part number 1540 was used.

Samples were tested according to the Horizontal Flame Test and Self-Extinguishing Test methods, described herein and reported in Table 1.

Example 15

As depicted in FIG. 8, discrete dots of Polymer resin-Expandable graphite Mixture 1 (20) were printed on the exposed side of thermally stable convective barrier 1 (30′) of example 10. An additional layer of thermally stable convective barrier 1 (30″) was adhered to the convective barrier side of the two layer laminate by bringing the layers together in a nip. The gravure lamination was carried out substantially in the same manner as described in laminate example 1. The resulting exposed side of the second convective barrier 1 (30″) was printed with discrete dots of PR1 (40) and adhered to 60 gsm Aramid knit backer textile (50). The resultant laminate was a four layer laminate which was allowed to cure for about 48 hours at greater than about 50% relative humidity.

Samples were tested according to the Horizontal Flame Test and Self-Extinguishing Test methods, described herein and reported in Table 1.

Example 16

A three layer laminate was prepared substantially according to the laminate of Example 4, except that PR1 was used to prepare the two layer laminate portion of the three layer laminate, while polymer resin-expandable graphite mixture 1 was used to convert 2 L into 3 L laminate.

TABLE 1 Break Open After- Laydown MVTR Time Flame* Melt Sample (oz/yd2) (g/m2/day) (sec) (sec) Drip Laminate Example 1 1.2 >8000 >120 0 No Laminate Example 10 — >10000 6 20* Yes Laminate Example 2 1.0 >7600 >120 0 No Laminate Example 3 — >9300 >120 0 No Laminate Example 11 1.3 >7500 21 20* — Laminate Example 12 1.3 >11500 22 20* — Laminate Example 13 0.9 >9500 31 20* — Laminate Example 14 — — 3 20* — Laminate Example 15 — >7500 27 20* Yes Laminate Example 16 — — — 20* — Laminate Example 4 1.0 >8900 >120 0 No Laminate Example 5 1.0 >10300 >120 0 No Laminate Example 6 — — >60 0 No Laminate Example 7 — — >120 0 No Laminate Example 8 1.4 >7800 >120 0 No Laminate Example 9 0.9 >9400 >120 0 No *Sample continued to burn and had to be extinguished.

Examples 17 through 20

A series of examples were prepared using an alternate method. First a two layer laminate substantially comprising an ePTFE film and a 20 grams per square meter melt blown polyester non-woven was obtained from W.L. Gore and Associates, Inc. under part number NASZ100000C.

Next, a series of three layer laminates were constructed by laminating the two-layer laminate (NASZ100000C) to a second non-woven using a meltable adhesive web (part number PE2900 from Spufab, Ltd. Cuyahoga Falls, Ohio). The composition of each laminate made in accordance with this example is presented in Table 2. All of the three-layer laminates were produced in the following manner.

An amount of expandable graphite as indicated in the Table 2 was weighed and distributed evenly on the ePTFE surface of the two-layer laminate. An adhesive web weighing approximately 17 gsm was placed on top of the expandable graphite that was distributed on the two layer laminate. A second non-woven was placed over the adhesive web. Heat and pressure were applied to fuse the layers together at a temperature in excess of the adhesive melt temperature but below the expansion temperature of the graphite, approximately 163° C. and 40 psi for 15 seconds.

The Examples were tested for break-open time and after-flame time according to the methods described above. Comparison of Example 17 with Examples 18 and 19 shows the addition of expandable graphite has an improved break-open time; however, after-flame and melt dripping are inferior to Laminate Examples 1 through 9. The effect of construction method and materials is shown by comparison of Example 20 with Laminate Example 8. Both Example 20 and Laminate Example 8 have substantially the same laydown weight of the substantially the same expandable graphite; Laminate Example 8 has a longer break-open time, shorter after-flame, and no melt dripping.

TABLE 2 Expandable Break- Graphite Second Open After- Example Expandable Laydown Non-woven Time flame Melt No. Graphite (gsm) (Face) (sec) Time (sec) Dripping 17 None 0 Nylon 6 20* Yes 18 ES100C10¹ 4 Nylon 8 20* Yes 19 ES100C10¹ 8.5 Nylon 8.5 20* Yes 20 Nyagraph 351² 8.5 Nylon 14 20* Yes 20* indicates that the flame had to be extinguished ¹Source ES100C10-Graphit Kropfmühl AG ²Nyagraph 351-Nyacol Nano technologies, Inc Ashland, MA

Garment Flammability Tests on laminate jacket examples were conducted as per ASTM F1930-00 with heat flux of 2.0 cal/cm²-sec. Ensemble Lay-up as Cotton-T shirt & shorts, NyCo shirt and pants, and the Laminate Jacket.

TABLE 3 Total After- Percent flame Example Sample % 2^(ND) Degree % 3^(rd) Degree Body on Melt ID Description Burn Burn Burn (%) Laminate Dripping 21 Laminate 9.7 27 37 >120 sec    Yes Example 21 Jacket 22 Laminate 0 0 0 1 sec No Example 4 Jacket 23 Laminate 1.4 0 1.4 4 sec No Example 5 Jacket 24 Laminate 14 0 14 5 sec No Example 4 Jacket tested without NyCo shirt and pants

Examples 21 through 24

Example Jacket 21 was constructed using a three layer PTFE laminate (Part Number EXSH100050AZ available from W.L. Gore and Associates, Inc.) and without heat reactive material, and having the same meltable outer textile. Example Jackets 22, 23 and 24 were prepared from laminates made substantially according to Example 4 and Example 5. Each example jacket was tested under the Garment Flammability Test Method (such as that available at the test labs at North Carolina State University called Pyroman test) for Garment Flammability described above according to ASTM F1930-00 with heat flux of 2.0 cal/cm2-sec, for 4 second exposure as indicated in Table 3. Each example jacket was prepared so that the face textile faced direct flame exposure. Because jacket design may effect Garment Flammability Test performance, the jackets were designed so that zippers were covered from flame exposure. The Pyroman laminate jacket results shown in Table 3 indicate that the present invention may provide a percent body burn value that is 10 percentage points lower than a substantially similar jacket without the heat reactive material. The percent body burn value may be 20 percentage points lower than a substantially similar jacket without the heat reactive material. The after-flame may also be reduced by at least 100 seconds. The after-flame is reduced by at least 60 seconds. The after-flame is reduced by at least 30 seconds. The after-flame is reduced by at least 20 seconds. The after-flame is reduced by at least 10 seconds.

While particular embodiments of the present invention have been illustrated and described herein, the present invention should not be limited to such illustrations and descriptions. It should be apparent that changes and modifications may be incorporated and embodied as part of the present invention within the scope of the following heat reactive materials. 

1. A method of reducing the percent burn of a garment in a 4-second Garment Flammability Test (4-second Pyroman exposure) by at least 10% comprising: a) providing a textile composite comprising: a meltable outer textile comprising meltable material; a thermally stable convective barrier comprising expanded polytetrafluoroethylene or polytetrafluoroethylene; and a heat reactive material between the meltable outer textile and the thermally stable convective barrier, wherein the heat reactive material comprises a polyurethane-expandable graphite mixture; b) constructing a garment with an outer surface of said garment comprising said outer textile; and c) with the outer surface of the outer textile oriented toward a flame, subjecting the garment to a 4-second Pyroman exposure test, wherein the percent body burn is decreased by at least 10 percentage points in the 4-second Pyroman exposure test compared to a garment constructed without the heat reactive material between the meltable outer textile and the thermally stable convective barrier.
 2. The method of claim 1, wherein the polyurethane-expandable graphite mixture is applied as discrete dots that cover an area of less than 50%.
 3. The method of claim 1, wherein the polyurethane-expandable graphite mixture bonds the meltable outer textile and the thermally stable convective barrier.
 4. The method of claim 1, wherein the polyurethane-expandable graphite mixture comprises less than 50 wt % of the expandable graphite.
 5. The method of claim 1, wherein upon exposing the meltable outer textile to heat sufficient to melt said meltable outer textile, the heat reactive material expands and absorbs the melt of said meltable outer textile, forming a composite of said meltable outer textile and said expanded heat reactive material.
 6. The method of claim 1, wherein said expandable graphite has an expansion of at least 900 μm upon heating to about 280° C.
 7. The method of claim 1, wherein an outer surface of said meltable outer textile has an afterflame time of less than 15 seconds.
 8. The method of claim 1, wherein the textile composite has a break-open time that is at least 20 seconds greater than the break-open time of the meltable outer textile without a heat reactive material.
 9. The method of claim 1, wherein said meltable outer textile consists of said meltable material. 